海盐氯循环对输送污染物致酸的缓冲作用

着重研究海盐氯循环对输送污染物致酸的缓冲作用,通过对全球低污染点酸雨资料分析,初步结论是:海盐氯循环使经过海洋上空输送的致酸大气污染物转化为中性盐,这一机制缓冲了经过海洋上空输送的致酸前提物的酸性,使受体点降水中出现氯亏损、硫富集,并伴随有降水中氯亏损和H+离子浓度的负相关。在高氯亏损降水样品中,降水pH值一般大于5.0。硫同位素动力学分析表明,当降水pH值大于5.6氯亏损时,污染物在海洋上空输送过程中和海盐发生非均相反应的速率与其发生均相反应的速率接近。但这一机制仅适用沿海地区。     

Analysis of bulk precipitation chemistry in Serbia for the period from 1982 to 2010

Bulk precipitation samples collected daily through bulk collectors at eight meteorological stations in Serbia were analyzed for their chemical composition. The data covers time series, from 20 to 28 years, in the period between 1982 and 2010. The most abundant ion in the samples was sulfate. Only 0.17 % of all samples were from strong acid rains (pH < 3.5). The relatively high average pH values (5.94–6.26) of the collected precipitation indicate the neutral or alkaline nature of local rainwater. Trends in both the annual amount and the composition of precipitation were tested by the nonparametric Mann–Kendall test and Sen’s slope estimator. Significant increasing trend of precipitation was identified for almost all stations. Rebuilding activities after the bombing of Serbia in 1999 were identified as a possible anthropogenic cause of the sharp increase of some ions (Ca²⁺) in the first year following the bombing. The origin of air masses arriving at one particular station was examined using two-dimensional backward trajectories. Western sectors (W, SW and NW) accounted for almost half (44.3 %) of all rainy days, while eastern sectors (SE, E and NE) brought only 10.4 % of all rainy days. The distribution, per sector, of volume-weighted concentrations of sulfate, nitrate, ammonium, calcium, potassium, magnesium, chloride and sodium ions, as well as the amount of precipitation and its pH values for one station, was also analyzed. Rainwater from the SE and S sectors was the most polluted.     

Some observations on the acidity and composition of rainwater in Sydney,Australia, during the summer of 1980–81

During the summer of 1980–81, a rudimentary form of wet-only event sampling was employed to collect a total of 294 rainwater samples at 12 sites spread across the metropolitan region of Sydney, Australia's largest city. From the samples were determined conductivity, pH, ammonium, chloride and nitrate ion concentrations as well as deposited water volume. Supplementary data consisting of city-wide averaged SO₂, NO₂, NO, and O₃ concentrations and 950 mb wind speed and direction were obtained for times coinciding with the period during which each event occurred.The pH of rainwater upwind of the city and unaffected by urban/industrial emissions was found to be usually 5, whereas the volume-weighted mean pH of all the metropolitan samples was 4.4, indicating that local emissions significantly increased rainwater acidity in the near field. Time available for conversion of precursors to acids averaged 1–2 h only.Considerable day-to-day variability in rainwater composition was observed. Factors identified as contributing to this variability included precursor gas concentration, wind speed, wind direction, amount of water deposited per event and possibly time of day. These results show that physical/meteorological factors cannot be excluded from consideration if variance in rainwater composition data is to be explained.     

Precipitation Chemistry in Semi-Arid Areas of Southern Africa: A Case Study of a Rural and an Industrial Site

Experimental data on the precipitation chemistry in the semi-arid savanna of South Africa is presented in this paper. A total of 901 rainwater samples were collected with automatic wet-only samplers at a rural site, Louis Trichardt, and at an industrial site, Amersfoort, from July 1986 to June 1999. The chemical composition of precipitation was analysed for seven inorganic and two organic ions, using ion chromatography. The most abundant ion was SO₄ ^{2 –} and a large proportion of theprecipitation is acidic, with 98% of samples at Amersfoort and 94% at LouisTrichardt having a pH below 5.6 (average pH of 4.4 and 4.9, respectively). This acidity results from a mixture of mineral and organic acids, with mineral acids being the primary contributors to the precipitation acidity in Amersfoort, while at Louis Trichardt, organic and mineral acids contribute equal amounts of acidity. It was found that the composition of rainwater is controlled by five sources: marine, terrigenous, nitrogenous, biomass burning and anthropogenic sources. The relative contributions of these sources at the two sites were calculated. Anthropogenic sources dominate at Amersfoort and biomass burning at Louis Trichardt. Most ions exhibit a seasonal pattern at Louis Trichardt, with the highest concentrations occurring during the austral spring as a result of agricultural activities and biomass combustion, while at Amersfoort it is less pronounced due to the dominance of relatively constant industrial emissions. The results are compared to observations from other African regions.     

南海北部大气气溶胶水溶性成分谱分布特征

通过对南海腹地岛屿测站和南海北岸测站气溶胶样品中水溶性成分的分析，以及与华南大陆清洁测点和城市测点的对比，结果表明:海岛测点气溶胶总质量与诸离子浓度均大大低于海岸与大陆测点。其分布以三峰型出现的比较多，海岛与海岸气溶胶中水溶性成分以SO2-4，Cl-与Ca2+，Na+为含量比重最大的离子成分；与华南大陆测点相比，Cl-，Na+比重显著增加而NH+4的含量比重有所下降。     

广州气溶胶质量谱与水溶性成分谱的年变化特征

广州气溶胶质量谱与水溶性成分谱的年变化特征吴兑，陈位超（广州热带海洋气象研究所，广州，５１００８０）近年来，我们曾在粤、桂、琼三省华南广大地区采集并分析了大气气溶胶分级样品，从气溶胶参与雨水酸化过程，吸湿性气溶胶作为凝结核的作用，以及海岸地带吸湿性粒...     

广州地区春季污染雾的化学特征分析

使用2005年2～3月在广州地区采集的雾水样品资料,分析了广州地区污染雾雾水的化学组分;对3次典型污染雾过程雾水的离子浓度及其可能的来源进行了分析。广州地区的污染雾雾水中的诸离子浓度远高于雨水中的值,因而,雾不但造成视程障碍,而且是高浓度污染的液态颗粒物,对人体健康十分有害。在雾水中浓度最高的阴离子是SO4=, 其次是NO3-;在阳离子中Ca++、NH4+的浓度最高。雨水比雾水更酸,说明虽然雾水中的离子浓度较雨水高得多,但大量的离子成分中存在更多的缓冲物质,比如说NH4+和Ca++。雾水中的Ca++、SO4=、Mg++有明显的富集现象,广州地区的污染雾雾水主要受大陆环境和人类活动的影响。这期间广州地区出现严重污染雾与水汽充足和大量气溶胶污染粒子的存在直接有关。     

Precipitation chemistry and corresponding transport patterns of influencing air masses at Huangshan Mountain in East China

One hundred and ten samples of rainwater were collected for chemical analysis at the summit of Huangshan Mountain, a high-altitude site in East China, from July 2010 to June 2011. The volume-weighted-mean （VWM） pH for the whole sampling period was 5.03. SO2- and Ca2＋ were the most abundant anion and cation, respectively. The ionic concentrations varied monthly with the highest concentrations in winter/spring and the lowest in summer. Evident inter-correlations were found among most ions, indicating the common sources for some species and fully mixing characteristics of the alpine precipitation chemistry. The VWM ratio of [SO]-]/[NO3] was 2.54, suggesting the acidity of rainwater comes from both nitric and sulfuric acids. Compared with contemporary observations at other alpine continental sites in China, the precipitation at Huangshan Mountain was the least polluted, with the lowest ionic concentrations. Trajectories to Huangshan Mountain on rainy days could be classified into six groups. The rainwater with influencing air masses originating in Mongolia was the most polluted with limited effect. The emissions of Jiangxi, Anhui, Zhejiang and Jiangsu provinces had a strong influence on the overall rain chemistry at Huangshan Mountain. The rainwater with influencing air masses from Inner Mongolia was heavily polluted by anthropogenic pollutants.     

The degree of Cl-loss for the particulate matter (PM) and fog water sampled at the same air mass at the Hachimantai mountain range in northern Japan

It is well known that sea-salt aerosols in particulate matter (PM) react with acids such as H₂SO₄ and HNO₃ during transportation and thereby lose chloride ions (Cl-loss). The PM and fog were sampled concurrently at different altitudes in the Hachimantai mountain range, northern Japan. The PM and fog sampled at different altitudes had nearly identical properties for the ion components. However, the PM was in a Cl-depleted state (more than 80% of all samples), but the fog water was not in so Cl-depleted state (less than 29%). As a result, it could be explained that this phenomenon caused because the fog droplets took up the gaseous state HCl other than sea-salt PM. After all Cl^- in the fog water recovered and was rather rich compared with the sea-salt or the PM by the uptake of the gaseous state HCl. Moreover, it was found that for PM_coarse(2.5 < D < 10), 86% of the acid (H₂SO₄ and HNO₃) was consumed for Cl-loss reactions and/or for dissolution of Ca and Mg in soil particles.     

STUDY ON THE CHEMICAL CHARACTERISTICS OF POLLUTING FOG IN GUANGZHOU AREA IN SPRING

Samples of fog water collected in the area of Guangzhou during February, March and April of 2005 are used in this work to study the chemical composition of fog water in polluting fog there. Three typical episodes of polluting fog are analyzed in terms of ionic concentration and their possible sources. It is found that the concentration of various ions in fog water is much higher than those in rainwater. Fog not only blocks visual range but contains liquid particles that result in high degree of pollution and are very harmful to human health. SO₄⁼ is the anion with the highest concentration in fog water, followed by NO₃^-.For the cation, Ca⁺⁺ and NH₄⁺ are the highest in concentration. It is then known that rainwater is more acidic than fog water, indicating that ionic concentration of fog water is much higher than that of rainwater, but there are much more buffering materials in fog water, like NH₄⁺ and Ca⁺⁺. There is significant enrichment of Ca⁺⁺, SO₄⁼, and Mg⁺⁺ in fog water. In the Guangzhou area, fog water from polluting fog is mainly influenced continental environment and human activity. The episodes of serious fog pollution during the time have immediate relationships with the presence of abundant water vapor and large amount of polluting aerosol particles.     

GRADIENT DISTRIBUTION OF ACID RAIN IN THE SCENIC RESORT OF THE BAIYUN MOUNTAIN IN GUANGZHOU

1 INTRODUCTION Sitting in the central part of the Pearl River Delta, Guangzhou is one of the cities in China that are most polluted by acid rain. Broad attention has been brought to the problem. Since the early 1980s, a series of observation and studies h…     

广州白云山风景区酸雨梯度分布

对1999年白云山风景区1~10月的降水pH 值、化学成分以及1月、6月大气低层的气溶胶进行了监测.分析结果表明(1)白云山3个测点降水的平均pH值最低为4.83,最高为5.29;酸雨频率最低58 %,最高91 %;强酸雨频率最低19 %,最高39 %.降水酸度和酸雨频率呈梯度变化,pH值随高度增高而减小,酸雨和强酸雨频率增加.(2)冬季近地层大气中偏碱性气溶胶在白云山的组成比较稳定,山上和山下测点气溶胶水溶性离子成分基本一致;而夏季山上、山下的成分有所不同,山上的SO42-比例明显增大.另外,尽管气溶胶中NO3-的含量极少,但降水中NO3-有明显的富集现象.(3)白云山降水离子成分中SO42-占阴离子的比例最大、NO3-次之;Ca2+占阳离子的比例最大、NH4+稍低.随高度上升SO42-和Ca2+在降水中的比例有所下降,而NO3-和NH4+比例明显增加,NO3-和NH4+对山上降水酸度的影响是相对增大的.(4)受附近公路交通的直接影响,白云山降水中的NO3-比例较大,NO3-/SO42-当量浓度比值平均达到0.4;NO3-对白云山降水酸度有较大的贡献,而且这一贡献随高度而增大.     

Rainwater acidity and ion concentration correlations in a midwest storm system

The pH and the concentrations of sulfate, nitrate, ammonia, and calcium in rainwater were measured for two periods of a single midwest rainstorm which occurred over a mesometeorological network in central Illinois on 24–25 July 1979. Regression analysis was used to compare ion concentrations with rainfall amount, and ion balance was used to compare cation and anion concentrations at individual sites. Only the ions SO₄ ^2- and NO₃ ^- show any significant relationship to rainfall amount, decreasing as rainwater amounts increase (r=–0.57 and –0.60, respectively). During the first period of the rainstorm, a sequential sampler measurements allowed the calculation of detailed temporal variations in SO₄ ^2-, pH, and rain rate. SO₄ ^2- decreased, and pH increased as the rate increased and the opposite temporal pattern occurred as the rain decreased at the end of the period. Reasons for these variations are discussed.Research done while a visiting scientist at the Illinois State Water Survey, Champaign, Illinois, U.S.A.     

华南准静止锋暖区内降水的物理化学特征

介绍了一次华南准静止暖区内降水的物理化学特征的综合观测分析结果。主要有：①暖区内积云降水雨滴浓度不高，但滴径较大，谱型以多峰谱为主；②雨水ｐＨ值较低，平均４．４３，离子成分中ＮＯ３，Ｃｌ，ＳＯ４，ＮＨ＾＋４，Ｎａ＾＋的浓度较高；③本次降水清除了气溶胶总质量的４５％，对Ｃｌ，Ｆ，ＮＯ３的清除率较高；④由于气溶胶中阴离子被雨水清除的效率较高（主要是ＮＯ３）而阳离子的清除率低，致使雨水ｐＨ值下降，这可能     

Source identification and variation in the chemical composition of rainwater at coastal and industrial areas of India

Studies on precipitation chemistry were carried out to understand the nature and sources of rainwater at Rameswaram and NTPC Dadri, India representing coastal and industrial region during 2010. The rainwater samples, collected at these locations, were analyzed for major ions and pH. The data were assessed for its quality. The pH of rainwater at two locations varied from 5.53 to 6.73 and 5.1–6.6, indicating alkaline nature except a few acidic events. The dominance of Cl− and Na+ were observed in coastal environment whereas dominance of Ca2+ was seen in industrial environment. The nss-SO42- (37.9%) at Rameswaram is less influenced by anthropogenic activities whereas nss-SO42- (72.5%) at NTPC Dadri is influenced by pollutants emitted by anthropogenic sources. The ratio of H+/(NO3- + SO42-) was observed as 0.04 and 0.008 for Rameswaram and NTPC Dadri which is close to zero, indicate 99.99% of acidity was neutralized in precipitation. Ca2+, NH4+ and Mg2+ play an important role in neutralization of acidic ions in rainwater. For source identification, correlation matrix analysis was established, which showed that in general, at both sites; correlation between the acidic ions SO42- and NO3- indicating their origin from similar sources, because of the similarity in their behavior in precipitation and the co-emissions of their precursors SO2 and NOX. The correlation coefficient of (SO42- + NO3-) vs (Ca2+) at Rameswaram and NTPC Dadri were 0.77 and 0.87 indicates that CaCO3 is the major neutralizing agent for both the region. Overall, the influence of marine, terrestrial and anthropogenic sources was observed in the rain events.     

Using hourly measurements to explore the role of secondary inorganic aerosol in PM2.5 during haze and fog in Hangzhou,China

This paper explores the role of the secondary inorganic aerosol （SIA） species ammonium,NH4＋,nitrate,NO3-,and sulfate,SO24-,during haze and fog events using hourly mass concentrations of PM2.5 measured at a suburban site in Hangzhou,China.A total of 546 samples were collected between 1 April and 8 May 2012.The samples were analyzed and classified as clear,haze or fog depending on visibility and relative humidity （RH）.The contribution of SIA species to PM2.5 mass increased to ～50％ during haze and fog.The mass contribution of nitrate to PM2.5 increased from 11％ during clear to 20％ during haze episodes.Nitrate mass exceeded sulfate mass during haze,while near equal concentrations were observed during fog episodes.The role of RH on the correlation between concentrations of SIA and visibility was examined,with optimal correlation at 60％-70％ RH.The total acidity during clear,haze and fog periods was 42.38,48.38 and 45.51 nmol m-3,respectively,indicating that sulfate,nitrate and chloride were not neutralized by ammonium during any period.The nitrate to sulfate molar ratio,as a function of the ammonium to sulfate molar ratio,indicated that nitrate formation during fog started at a higher ammonium to sulfate molar ratio compared to clear and haze periods.During haze and fog,the nitrate oxidation ratio increased by a factor of 1.6-1.7,while the sulfur oxidation ratio increased by a factor of 1.2-1.5,indicating that both gaseous NO2 and SO2 were involved in the reduced visibility.     

新型消暖雾催化剂与传统吸湿性催化剂消雾性能的室内对比试验

为了研究一种新的环保型消暖雾催化剂RC／XW的消雾性能,同时选取无水氯化钙（CaCl2）和氯化钠（NaCl）2种吸湿性物质作为对比物,对它们进行室内试验研究。其中RC／XW粒子直径主要集中在12um;将无水氯化钙和氯化钠分别粉碎成10um、15um、20um和30um4个不同的直径。结果表明：不同种类的催化剂、同种类不同尺度的催化剂之间消雾效果都存在很大差异。消雾效果与播撒剂量直接相关。RC／XW适用于消除含水量在0．3g·m^-3以上的严重影响视程的暖雾,且播撒剂量要〉1g·m^-3。     

Wet deposition due to fog in the Po Valley,Italy

Wet deposition due to radiation fog is examined in this paper. The area where the reported measurements were performed, the Po Valley, northern Italy, is characterized by both a high fog occurrence during the fall-winter months and fog water solutions of high ionic concentration and acidity.Estimated wet deposition for NH ₄ ⁺ , NO _inf3 ^sup- and SO _inf4 ^sup2- ions due to fog droplet settling to the ground accounts for 13.2, 12.1 and 5.3 percent with respect to bulk precipitations over the same period: January–March and October–December (fog season).Fog deposition rates show that this process can be an important pathway of trace gases and particles loss from the air. First indicative results of fog removal efficiency with respect to air particulate matter are presented.Dry deposition parameters should be taken into account in evaluating the potential effect of fog droplet deposition on vegetation.     

Relationships Between Rainwater Composition and Synoptic Weather Systems Deduced from Measurement and Analysis of Hong Kong Daily Rainwater Data

The composition of Hong Kong rainwater has been studied in the context of seven types of prevailing synoptic weather system. These represent different precipitating airmass origins in terms of continental, maritime, local or mixed sources. Replicate sampling was performed on a daily basis from 1994–1995 for both bulk deposition (n = 60) and simultaneous wet deposition (n = 27) collectors. Reliable analytical data were obtained for the concentrations of the soluble components H+, Na+, Ca2+, K+, Mg2+, Cl-, NO3- and SO42-. The acidity of rainwater was found to be greater when Hong Kong was under the influence of an approaching cyclone (type AC), northeasterly monsoon (type NE) or cold front (type CF) than for prevailing easterly anticyclones (type E), southerly/southwesterly monsoon systems (type S), or cyclonic flows (type C). A common characteristic of occasions of acid rain in Hong Kong was the build-up of local pollutants under conditions of low windspeed, as shown by the significant correlation between rainwater pH and lognormal surface windspeed, but not windvector. The acidity of Hong Kong rainwater was thus largely determined by local sources, although the participation of a continental airmass was evident for some systems. The daily bulk deposition flux of H+ on rainy days varied by more than an order of magnitude from type C (0.2 meq m-2 d-1) to types AC, trough (T) and NE (>2 meq m-2 d-1).     

Precipitation Chemistry and Wet Deposition in Kruger National Park, South Africa

The chemical composition, as well as the sources contributing to rainwater chemistry have been determined at Skukuza, in the Kruger National Park, South Africa. Major inorganic and organic ions were determined in 93 rainwater samples collected using an automated wet-only sampler from July 1999 to June 2002. The results indicate that the rain is acidic and the averaged precipitation pH was 4.72. This acidity results from a mixture of mineral acids (82%, of which 50% is H₂SO₄) and organic acids (18%). Most of the H₂SO₄ component can be attributed to the emissions of sulphur dioxide from the industrial region on the Highveld. The wet deposition of S and N is 5.9 kgS⋅ha⁻¹⋅yr⁻¹ and 2.8 kgN⋅ha⁻¹⋅yr⁻¹, respectively. The N deposition was mainly in the form of NH₄ ⁺. Terrigenous, sea salt component, nitrogenous and anthropogenic pollutants have been identified as potential sources of chemical components in rainwater. The results are compared to observations from other African regions.